Esters of 2, 2, 4, 4-tetranitrobutanol



United States Patent ree 2,978,455

The esters of dinitroethanol which are operable in 2,978,455 I 5 these reactions are not limited to any specific types, hence ESTERS F Z,Z,4,4 TETRANHROBUTANOL R may be any alkyl, alkenyl, aryl, alkaryl, cycloalkyl t or heterocyclic group. The esters may be formates, Milton B. Frankel Pasadena Calif. assignor to Aero et- GePeral p a o C a corporation of aceates, propronates, butyrates, benzoates, toluates, ohm carboxylates, picolinates, cyclohexylcarboxylates, cyclo- No Drawing. Filed Oct. 22, 1956, Ser. No. 617,667

hexylacetates, etc. 14 Clainm (CL Examples of the manner in which the reactions occur are set forth by the following specific examples; This invention relates to new compositions of matter 1 Formation of 2-br0m0-2,2-dinitr0ethyl acetate and specifically to esters of 2,2,4,4-tetranitrobutanol and enol salts of esters of 2,2,4,4rtetranitrobutanol, and has I gi'g g g f i'g gsg g g gii h z gg l g i ggg f for its object, the formation of esters of 2,2,4,4-tetranitropp 1 1 gr ms butanol and derivatives thereof. 15 gotassllum hT gg pf 2 em 5 mo A related object of the invention is to provide a new ii g 8., g 2 g g: 1 3

process for the preparation .of esters of 2,2,4,4-tetranitrov; r

- p of bromine-1s added durmga forty minute period. The

Y li i 5 53;123:33 1? a c hi i hhh riii i h ggf zi g reaction mixture is extracted with several portions of 20 ether. The etherextracts are combined, washed twice 33 5 3 i figz z fi Hal filed January with water, and dried over sodium sulfate at 0 C- The Tiie compositions of this invention find valuable use ether Solution'is concentrated and distilled at betwcien Patented Apr. 4, 1961 phthalates,.naphthalates, phenylaeetates, oleates, pyroleas explosives and as plasticizers for polymeric resins and under 2 pressure The dl'stlnate I bromo-2 SZ-dinitroethanol is a white mushy solid which" plastics. The esters of 2,2,4,4-tetran1trobutanol are highly I sensitive compositions. Certain of the metal salts thereof becomes hquld on Contact wlth moist The 2,2-dinitroethanol is reacted immediately with a solution figgfifigg g: havmg a sens" v of 86 grams 1.1 mole)\'of acetyl chloride dissolved in Thesecompositions also find valuable use as intersoo'ml'bf dry 9 The.soluuon refiuxefl for mediates in the production of alcohols and acids which hours to allow complete reacnon' The solvent is are useful as components of propellant fuels. Both the 30 moveddunder reduced pr'essure" leavmg a hght yellow o a w free esters and the salts of this invention will readily hquld which Is distilled at between 86 95 undcr react with formaldehyde to form their corresponding {15:3 gffig alcohols. Similarly, both the salts and the free esters f f 4760' th I will also condensle with an agtenoic acid ester in basic 21, 2 f gf g :2 25;; bn -i gg solution to yieldt e correspon ing acids. V 7

It is well known in the art that compounds containing analysis the bmmmhe cqfltent of the compouni f u a bromodinitromethyl group will react quantitatively to be 3096 n .emirogen in was with an iodide salt, such as sodium and potassium iodide, Formationof potassium 2,2,4,4-tetranitr0butyl acetate to liberate free iodine in quantities molecularly equiva- 40 A smacked flask ovi de d i mechanical stirrer lent to the amount of bromine in the molecules. This is and dropping funnel charged with 514 grams (2 normally Illustrated by the followmg equatlon: moles) of 2-bromo 2, 2-dinitroethyl acetate dissolved in N01 '2 liters of methanol. The solution is cooled to'O and j a solution of 1660 grams (10 moles) of potassium. iodide No in 3000 ml. of aqueous methanol, preferably methn 45 anol,,is added. The purple reaction mixture is filtered where R is any organic rad1cal and M is any cation that 1 ga yellow solid separates out, The yellow .forms an lodlde Soluble; & elther Water or orgamc "solid is washed with ether until free of iodine. The yelsolvent. The preferred iodides are those of sodium, am-

low solid thus'formed is potassium 2,2 ,4,4-tetranitro momum, potassium, lith um, calcium, Stl'OlltlllIIl, 'mag nesium, barium and aluminum.

It should be expected from the prior art that when an ester of 2-bromo-2,2-dinitroethanol is treated with.

equivalent" to 377-grams. The compound indicated 'a melting point of 174" C., ho-wever,.this temperatureis,

only approximate, since the compound exploded at suban iodide salt, one" should expect the formation of free tion scheme set forth below:

iodine and an aci-salt of an ester of 2,2-dinitroethanol inaccordance with the general reaction scheme set forth: 55 above; however, I have discovered that the reactioridoes purified by recrystallizing it from water, the potassium butyl' acetate; 1 The yield obtained by this methodis' stantially the melting temperature. The product may be;

salts of'the compound being substantially insoluble in water. "The theoretical. composition of C H N O K is: TV not occur in the anticipated manner and that anew and totally unexpected product is obtained. According to I i -%.C 21-56; 211; 1 .I my discovery, the'expected aci-saltof the 'ester of"2,2-.

.5. %CL l 3. Q r 7 31 2 tanpl ispbtainemin accordance with thei-general r'eaca Formation of 2,2,4,4 tetranitrobutyl acetate Ina .3j-necked flask fitted witha mechanical ,jstirre'r, thermometer, andfdroppingfunnel; are,'placed' "grains (0134*mole) of"'pot'assium '2, 2,4", 4-'tetrzfnitrobutyl acetate p in 1500 ml. of water. Thesuspension is cooled to 0 0 W N and a solution of 5 0 of sulfuric acid and 300 ml. of

instead; the aci-salt ofan esterof 2,2 ,4,4-t etranitrobu No. 7 $911. i rin is, a qq f ran t st hour t q nsure m 1e reaction and'tlie mixture is'l'filter'eda- TheT-cfr'ea" lo The ehmpon hrs determined by ultimate analysis'showedi dinitroethanol is notvformed' as an end product, but '60. n

water. is added'carefulli l fith 9d. of the addition 5 the reaction mixture will turn from orange to yellow.

solid which is collected on the filter is washed well with water and air dried. The yield of 2,2,4,4-tetranitrobutyl acetate is 70.0 grams (67.5%) yield. The reaction involved is as follows:

%C, 24.33; %H, 2.72; %N, 18.92

An ultimate analysis gave the following results:

%c, 24.62; %H, 2.89; %N,'13.50

2. As new compositions of matter, the esters of 2,2,4,4-

tetranitrobutanol having the general formula:

, wherein R is a lower alkyl radical.

3. As new compositions of matter, the esters of 2,2,

4,4-tetranitrobutanol having the general formula:

wherein R is an alkenyl radical.

15 4. As new compositions of matter, the esters of 2,2,

4,4-tetranitrobutanol having the general formula:

wherein R is an aryl hydrocarbon radical.

5. As new compositions of matter, the esters of 2,2,

By substituting any other acid halide for the acetyl 4.4-tetranitrobutanol having the general formula:

chloride used in the preparation of 2-bromo-2,2-dinitro- N02 NO ethyl acetate in the above examples, for example, the alkanoic halides such as propionyl chloride, n-butyryl H"CI7 CHT?TCHQ O CTR t bromide, n-valeryl chloride, n-capronyl chloride, etc.; N02 N0 the alkenoic acid chlorides such as acrylyl chloride, wherein R is a hetemc I yclic radical.

furnaiyl chloride Oleyl chloride the aromatic a 6. As a new composition of matter, 2,2,4,4-tctranitrochlorides such as benzoyl chlorlde, toluyl chloride, but 1 t t h th t t l f 1 phthalyl chloride, cinnarnyl chloride, naphthalyl ch10 y a a e avmg e 5 0mm ride; the heterocyclic acid chlorides such as furanyl chlo- N01 N01 ride, pyrrole oi carboxylicacid chloride, picolinyl chloride, nicotinyl acid chloride, ,etc.; the cycloalkyl acid 05 T chlorides such as hexahydrobenzoyl chloride; the corre- Spending tetranitrobutyl esters and ts h I 7. As a new composition of matter, potassium tetray, i fiA- ly P P Y nitrobutyl acetate having the structural formula: valerate, n-capronate, acrylate, fumarate, oleate, benzoate, toluate, phthalate, cinnamate, naphthalate, furanate, f H pyrrole on carboxylate, picolynate, nicotinylate and hexa- K'C CH2CCH2'O-C-OIIH hydrobenzoate, respectively, will be obtained by proceed- N02 ing in the manner disclosed in the above examples, the acid portion of the composition being dependent upon The methqd of p p g t rs of 2,2,4,4 -tetrathe particular starting material used. It will be appreci- 5 mtmbutanoi i 9 Pompnses reactmfl an morgamc ated that in the case of dibasic acid halides such as Soluble lodlde with an ester havmg the general phthalyl chloride, a di-ester will beobtainedf mula:

The nitro compounds of this invention are useful as NO: high explosives and can be used many conventional explosive missile, projectile, rocket, or the like, as the main, explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162, issued y 17, 1949 One y Of using h explosives sisting of a lower alkyl, alkenyl, arylalkyl, allcylaryl, of this invention in a device such as that disclosed in aromatic hydrocarbon, cycloalkyl, and heterocyclic rad-- United States Patent No. 2,470,162, is to pack thecrystal- 5 i 1 line explosive in powder form into the warhead of the 9, Th h d of preparing esters of 2 2 4,4. missile Alternatively, the Crystals eail be first Pelletiled nitrobutanol which comprises reacting an inorganic waand then packed. A charge thus prepared is sufficiently ter'soluble iodide with an ester having the general insensitive to withstand the shock entailed in the ejection f l of a shell from a gun barrel or from a rocket launching V O N 1 tube under the pressure developed from ignition of a u I propellant charge, and can be caused toexplode on 'T wherein R is a radical selected from the group con- 1 operation of an-impactor time fuse-mechanism firing a V a N02 n t 0 g g gg exposlve a .lead az'lde or mercury wherein R isa loweralkyl radical.

I m, 10. The method of preparingfester's of 2,2,4,4-tetranitrobutanol which comprises reacting an inorganic wa- 1. As new compositions of matten'the salts of esters oi 22,4,44etmnitmbutanol having the gneiral fgmimlaiter soluble iodide with an ester having the general forwherein R is a lower alkylfradicaland X is anjalkali, I wherein R an alkenyl radical. metal radical.

i r'ing' 2,2,4A-tetrahitrobutyl 11. The method of'pr 5 wherein X is a radical selected from the group consisting of hydrogen, ammonium and metals which are capable of forming water soluble iodides, and R is a radical selected from the group consisting of lower alkyl, alkenyl, aromatic hydrocarbon, arylalkyl, alkylaryl,

10 cycloalkyl, and heterocyclic radicals.

References Cited in the file of this patent B.I.O.S. Final Report No. 709, item No. 22. The Production of Tetranitromethane and Nitroform. Re-

15 ported by W. Hunter, July 3, 1946. Page 8. 

5. AS NEW COMPOSITIONS OF MATTER, THE ESTERS OF 2,2, 4,4-TETRANITROBUTANOL HAVING THE GENERAL FORMULA: 